KR102204760B1 - Liquid crystal composition, optical film, polarizing plate, and image display device - Google Patents

Abstract

It is an object of the present invention to provide a liquid crystal composition that is excellent in orientation and has a good surface shape of an optically anisotropic layer to be formed and also has good adhesion to a polarizer, an optical film, a polarizing plate, and an image display device using the same. The liquid crystal composition of the present invention is a liquid crystal composition containing a copolymer having a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II), and a liquid crystal compound.

Description

Liquid crystal composition, optical film, polarizing plate, and image display device

The present invention relates to a liquid crystal composition, an optical film, a polarizing plate, and an image display device.

It is known that a polarizing plate is used as a member such as a liquid crystal display (LCD) and an organic light emitting diode (OLED), and plays an important role in its display performance.

Further, as for a general polarizing plate, a configuration in which an optical film is bonded to one or both surfaces of a polarizer in which a dichroic dye such as an iodine complex is adsorbed and oriented with a polyvinyl alcohol (PVA) resin is adopted.

As an optical film attached to a polarizer, an optical film having an optically anisotropic layer (phase difference layer) in which a liquid crystal compound is aligned on a support such as triacetylcellulose (TAC) and the alignment state is fixed is known.

Moreover, as for the polarizing plate using such an optical film, the structure which bonded the polarizer and the support body of an optical film using adhesives, such as a polyvinyl alcohol system, was common.

Recently, from the viewpoint of increasing the wide viewing angle and thinning of the polarizing plate, a configuration in which a polarizer and an optically anisotropic layer of an optical film are bonded, or a configuration in which a support is peeled after bonding a polarizer and an optically anisotropic layer of an optical film has been proposed ( For example, see Patent Document 1, etc.).

Patent Document 1: International Publication No. 2014/199934

The inventors of the present invention examined the bonding of the polarizer described in Patent Document 1 and the optically anisotropic layer of the optical film, and formed according to the type of additive added from the viewpoint of the orientation of the liquid crystal compound and the planar shape of the optically anisotropic layer. It was clarified that the optically anisotropic layer to be formed becomes hydrophobic, and generally there is a case in which the adhesiveness with a hydrophilic polarizer is poor.

Accordingly, the present invention makes it a subject to provide a liquid crystal composition having excellent orientation, good surface shape of the formed optically anisotropic layer and good adhesion to a polarizer, an optical film, a polarizing plate, and an image display device using the same. .

The present inventors, as a result of intensive examination in order to achieve the above object, showed that by using a liquid crystal composition containing a copolymer having two or more predetermined repeating units, the alignment property was excellent and the surface shape of the formed optically anisotropic layer was good. It was found that it became, and the adhesiveness with a polarizer also became favorable, and this invention was completed.

That is, it discovered that the said subject can be achieved by the following structure.

[1] A liquid crystal composition containing a copolymer having a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II), and a liquid crystal compound.

[Formula 1]

Here, in formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ² -, -NR ² COO-, -CR ² N-, a substituted or unsubstituted divalent aliphatic group , A substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of combinations thereof, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or -X ¹ -P ¹ . P ¹ represents a polymerizable group.

In addition, in formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, substituted Or it represents an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R ¹¹ and R ¹² may be connected to each other via an alkylene linking group, an arylene linking group, or a linking group composed of a combination thereof. X ¹⁰ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ¹³ -, -NR ¹³ COO-, -CR ¹³ N-, a substituted or unsubstituted divalent aliphatic group , A substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof, and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[2] The liquid crystal composition according to [1], in which the copolymer further has a repeating unit represented by the following formula (III).

[Formula 2]

Here, in formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ²¹ represents an alkyl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a monovalent organic group including -Si(R ^a3 )(R ^a4 )O-, and R ^a3 and R ^a4 each independently represent an alkyl group, a haloalkyl group, or an aryl group. L ²⁰ represents a divalent linking group selected from the group consisting of -O-, -COO-, -OCO-, divalent aliphatic groups, and combinations thereof.

[3] The liquid crystal composition according to [2], wherein R ²¹ in Formula (III) is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

[4] The liquid crystal composition according to [3], in which the repeating unit represented by formula (III) is a repeating unit represented by the following formula (IV).

[Formula 3]

Here, in formula (IV), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ma and na each independently represent the integer of 0-19. However, ma and na represent the integer of 0-19 in total. X ²¹ represents a hydrogen atom or a fluorine atom.

[5] In the copolymer, the content of the repeating unit represented by formula (I) is 10 to 50 mass% with respect to all repeating units, and the content of the repeating unit represented by formula (II) is 5 to 50 mass with respect to all repeating units. %, and the content of the repeating unit represented by Formula (III) is 10 to 60 mass% with respect to all repeating units, the liquid crystal composition according to any one of [2] to [4].

[6] [1] to [5] wherein the polymerizable group represented by P ¹ in the formula (I) is any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-7) ] The liquid crystal composition according to any one of.

[Formula 4]

Here, in formulas (P-1) to (P-7), * represents a bonding position with X ¹ . R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two R ³ may be the same or different, and may be connected to each other to form a ring structure.

[7] The liquid crystal composition according to any one of [1] to [6], in which the copolymer further has a repeating unit represented by the following formula (V).

[Formula 5]

Here, in formula (V), R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[8] The liquid crystal composition according to any one of [1] to [7], wherein the liquid crystal compound is a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound having a polymerizable group.

[9] The liquid crystal composition according to any one of [1] to [8], further containing 0.5 to 7.0 mass% of a compound represented by the following formula (VI) with respect to the liquid crystal compound.

(Z)_n-L¹⁰⁰-(Q)_m (VI)

Here, in the formula (VI), Z represents a substituent having a polymerizable group, n represents an integer of 0 to 4, and when n is 2 or more, 2 or more Z may be the same or different. Q represents a substituent containing at least one boron atom, m represents 1 or 2, and when m is 2, two Qs may be the same or different. L ¹⁰⁰ represents an n+m valent linking group. However, when n is 0 and m is 1, L ¹⁰⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyneyl group, a substituted or unsubstituted aryl A group or a substituted or unsubstituted heteroaryl group.

[10] An optical film having an optically anisotropic layer obtained by polymerizing the liquid crystal composition according to any one of [1] to [9].

[11] The optical film according to [10], which has a support and an optically anisotropic layer provided on the support.

[12] The optical film according to [11], in which the copolymer contained in the liquid crystal composition according to any one of [1] to [9] is unevenly distributed on the air interface side of the optically anisotropic layer.

[13] The optically anisotropic layer is an optically anisotropic layer obtained by polymerizing the liquid crystal composition according to [9],

The optical film according to [11] or [12], in which the compound represented by formula (VI) contained in the liquid crystal composition according to [9] is unevenly distributed on the support side of the optically anisotropic layer.

[14] The optical film according to any one of [11] to [13], wherein the support is a cellulose acylate film or a cycloolefin film.

[15] Having the optical film according to any one of [10] to [14] and a polarizer,

A polarizing plate in which an optically anisotropic layer and a polarizer contained in an optical film are bonded together through an adhesive layer.

[16] An image display device comprising the optical film according to any one of [10] to [14], or the polarizing plate according to [15], and an image display element.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in orientation, and the surface shape of the optically anisotropic layer to be formed becomes favorable, and the liquid crystal composition which also improves adhesiveness with a polarizer, an optical film, a polarizing plate, and an image display device using the same can be provided.

Hereinafter, the present invention will be described in detail.

The description of the constitutional requirements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In addition, in this specification, the numerical range shown using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.

In addition, "(meth)acrylate" is used in the meaning of "any one or both of an acrylate and a methacrylate". The same applies to (meth)acrylic acid, (meth)acrylamide, and (meth)acryloyl groups.

[Liquid crystal composition]

The liquid crystal composition of the present invention is a liquid crystal composition containing a copolymer having a repeating unit represented by formula (I) described later and a repeating unit represented by formula (II) described later, and a liquid crystal compound.

In the present invention, as described above, by using a liquid crystal composition containing a copolymer having a repeating unit represented by formula (I) described later and a repeating unit represented by formula (II) described later, it is excellent in orientation and formed The surface shape of the optically anisotropic layer to be obtained becomes good, and the adhesiveness with the polarizer also becomes good.

Although this is not clear in detail, the present inventors estimate as follows.

That is, the repeating unit represented by the formula (I) contained in the copolymer contributes to the crosslinking reaction with the liquid crystalline compound, and the repeating unit represented by the formula (II) contained in the copolymer is affinity with the surface of the polarizer. By contributing to the property, it is considered that the orientation of the liquid crystal compound becomes good, the surface shape of the optically anisotropic layer to be formed becomes good, and the adhesiveness with the polarizer is also improved.

Hereinafter, each component of the liquid crystal composition of the present invention will be described in detail.

[Copolymer]

The copolymer contained in the liquid crystal composition of the present invention (hereinafter, also formally abbreviated as "polymer compound of the present invention" in the present specification) is a repeating unit represented by the following formula (I) (hereinafter also referred to as "part I"). Group) and a repeating unit represented by the following formula (II) (hereinafter, also abbreviated as "II part").

In addition, it is preferable that the polymer compound of the present invention has a repeating unit represented by the following formula (III) (hereinafter, also abbreviated as "III part").

In addition, it is preferable that the polymer compound of the present invention has a repeating unit represented by the following formula (V) (hereinafter, also abbreviated as "V part").

[Formula 6]

<Part I>

Part I of the polymer compound of the present invention is a repeating unit represented by the following formula (I).

[Formula 7]

In the formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable. And a hydrogen atom or a methyl group is more preferable.

Moreover, in said formula (I), X ¹ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ² -, -NR ² COO-, -CR ² N-, A substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of combinations thereof, R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, Or -X ¹ -P ¹ is represented. Also, P ¹ in the case where R ² is -X ¹ -P ¹ is the same as P ¹ in the above (I), represents a polymerizable group.

Here, as the substituted or unsubstituted divalent aliphatic group represented by X ¹ , for example, an alkylene group having 1 to 20 carbon atoms which may have a substituent or a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent (e.g. For example, cyclohexylene group) etc. are mentioned, Among them, an alkylene group having 1 to 15 carbon atoms is preferable, an alkylene group having 1 to 8 carbon atoms is more preferable, and a methylene group, ethylene group, propylene group, butylene Groups are more preferred.

Further, examples of the substituted or unsubstituted divalent aromatic group represented by X ¹ include a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent. As a divalent aromatic hydrocarbon group, for example, one hydrogen atom from two carbon atoms constituting the ring structure of an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triphenylene ring, and a fluorene ring. Groups obtained by excluding are mentioned, and among them, a phenylene group or a naphthylene group obtained by excluding one hydrogen atom from two carbon atoms constituting the ring structure of a benzene ring or a naphthalene ring is preferable. On the other hand, as a divalent aromatic heterocyclic group, an aromatic heterocycle such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, an oxadiazole ring, a thiazolothiazole ring, and a phenanthroline ring Groups obtained by excluding one hydrogen atom each from two carbon atoms constituting the ring structure of

As a substituent which may have a divalent aliphatic group or a divalent aromatic group, for example, a halogen atom, a hydroxyl group, an amino group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, a carboxyl group, a cyano group , -X ¹ -P ¹ , or with these, -O-, -S-, -COO-, -OCO-, -CONR ² -, -NR ² COO-, -HC=CH- and -CR ² N- And groups in which any one or more of them are combined. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or -X ¹ -P ¹ . Also, P ¹ in the case where R ² is -X ¹ -P ¹ is the same as P ¹ in the above (I), represents a polymerizable group.

The alkyl group having 1 to 20 carbon atoms represented by R ² described above is preferably an alkyl group having 1 to 6 carbon atoms, and specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isoview And a butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

Moreover, in said formula (I), P ¹ represents a polymeric group.

In the present invention, the polymerizable group represented by P ¹ in the formula (I) is preferably any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-7), Among them, it is more preferable that it is any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-3), and polymerization represented by the following formula (P-1) or (P-2) The penis is more preferred.

[Formula 8]

In the formulas (P-1) to (P-7), * represents the bonding position with X ¹ . R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two R ³ may be the same or different, and may be connected to each other to form a ring structure.

Moreover, as a C1-C5 alkyl group represented by R<^3> , specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, etc. are mentioned, for example.

In the present invention, from the viewpoint of ease of production, economy, and radical polymerization, as for the repeating unit represented by the formula (I), R ¹ in the formula (I) is a hydrogen atom or a methyl group, and in the formula (I) X ¹ is a divalent link selected from the group consisting of a combination of -O-, -COO-, -OCO-, and a substituted or unsubstituted divalent aliphatic group (preferably, an alkylene group having 2 to 8 carbon atoms) Group repeating units are preferred.

Specific examples of the repeating unit represented by the above formula (I) include, for example, a repeating unit represented by the following formula.

[Formula 9]

In the present invention, the content of the repeating unit represented by the formula (I) is preferably 5 to 80% by mass, more preferably 7 to 70% by mass, and 10 to 50% by mass with respect to all repeating units. It is more preferable.

<Part II>

Part II of the polymer compound of the present invention is a repeating unit represented by the following formula (II).

[Formula 10]

In the formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable. And a hydrogen atom or a methyl group is more preferable.

Moreover, in said formula (II), X ¹⁰ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ¹³ -, -NR ¹³ COO-, -CR ¹³ N-, Represents a divalent linking group selected from the group consisting of a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, and combinations thereof, and R ¹³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Show.

Here, as the divalent aliphatic group and the divalent aromatic group represented by X ¹⁰ , the same ones as those described for X ¹ in the above formula (I) are exemplified, and further, R ¹³ represents, having 1 to 20 carbon atoms. Examples of the alkyl group include those similar to R ² described in connection with the formula (I).

In addition, in the formula (II), R ¹¹ and R ¹² are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl Represents a group, and R ¹¹ and R ¹² may be connected to each other through a linking group composed of an alkylene linking group, an arylene linking group, or a combination thereof.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R ¹¹ and R ¹² include an alkyl group, an alkenyl group, or an alkynyl group which may have a substituent.

As the alkyl group, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexade Sil group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group , A linear, branched, or cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, and a 2-norbornyl group.

Specific examples of the alkenyl group include straight chains such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, and 1-cyclohexenyl group. , Branched or cyclic alkenyl groups.

Specific examples of the alkyneyl group include an ethanyl group, a 1-propyneyl group, a 1-butyneyl group, and a 1-octaynyl group.

Examples of the substituted or unsubstituted aryl group represented by R ¹¹ and R ¹² include those in which 1 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated 5-membered ring form a condensed ring, Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and a pyrenyl group are mentioned.

As the substituted or unsubstituted heteroaryl group represented by R ¹¹ and R ¹² , for example, 1 hydrogen atom on a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Excluding dogs, what made it a heteroaryl group is mentioned.

As a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxa Sol, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranyl, benzi Sooxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinazaline, naphthyridine, phenanthrol Lin, pteridine, etc. are mentioned.

Examples of the substituents R ¹¹ and R ¹² may have include monovalent non-metal groups excluding hydrogen, and for example, they are selected from the following substituent groups Y.

(Substituent group Y)

Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group , N-alkylamino group, N,N-dialkylamino group, N-arylamino group, N,N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group , N-arylcarbamoyloxy group, N,N-dialkylcarbamoyloxy group, N,N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group , Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N',N'-dialkylureido group, N'-arylureido group, N',N'- Diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group , N',N'-dialkyl-N-alkylureido group, N',N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-aryl Ureido group, N',N'-diaryl-N-alkyl ureido group, N',N'-diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkylureido group, N '-Alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N -Aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugated base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N -Alkyl carbamoyl group, N,N-dialkylcarbamoyl group, N-aryl carbamoyl group, N,N-diarylcarbamoyl group, N-alkyl-N-aryl carbamoyl group, alkylsulfinyl group, arylsulphine Diary, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N,N-di Alkylsulfinamoyl group, N-arylsulfinamoyl group, N,N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl Group, N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acyl Sulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonyl sulfamoyl group (-SO ₂ NHSO ₂ (aryl) ) And its conjugated base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (aryl)) and its conjugated base group , Alkoxysilyl group (-Si(Oalkyl) ₃ ), aryloxysilyl group (-Si(Oaryl) ₃ ), hydroxysilyl group (-Si(OH) ₃ ) and its conjugated base group, phosphono group (-PO ₃ H ₂ ) and its conjugated base group, a dialkylphosphono group (-PO ₃ (alkyl) ₂ ), a diarylphosphono group (-PO ₃ (aryl) ₂ ), an alkylarylphosphono group (-PO ₃ ( alkyl)(aryl)), a monoalkylphosphono group (-PO ₃ H(alkyl)) and its conjugated base group, a monoarylphosphono group (-PO ₃ H(aryl)) and its conjugated base group, phosphonooxide Group (-OPO ₃ H ₂ ) and its conjugated base group, dialkylphosphonooxy group (-OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphono Oxy group (-OPO ₃ (alkyl)(aryl)), monoalkylphosphonooxy group (-OPO ₃ H(alkyl)) and its conjugated base group, monoarylphosphonooxy group (-OPO ₃ H(aryl)) And the conjugated base group, cyano group, nitro group, aryl group, alkenyl group, and alkynyl group, and these substituents may be combined with each other or substituted hydrocarbon groups, if possible, to form a ring.

It is preferable that R ¹¹ and R ¹² in the formula (II) are hydrogen atoms or are connected to each other by an alkylene linking group.

Specific examples of the monomer forming the repeating unit represented by the formula (II) include monomers represented by the following formulas II-1 to II-12.

[Formula 11]

In the present invention, the content of the repeating unit represented by the formula (II) is preferably 3 to 80% by mass, more preferably 4 to 70% by mass, and 5 to 50% by mass with respect to all repeating units. It is more preferable.

<Part III>

It is preferable that the polymer compound of the present invention has a repeating unit (III part) represented by the following formula (III) from the reason that the adhesion of the formed optically anisotropic layer to the polarizer becomes better.

Here, the reason why the adhesiveness becomes better is that by having part III, the copolymer is unevenly distributed on the air interface side of the optically anisotropic layer to be formed (the side of the adhesive side with the polarizer), so that the II part of the copolymer is It is thought that it is because it became easy to interact with the surface of a polarizer.

[Formula 12]

In the formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable. And a hydrogen atom or a methyl group is more preferable.

In addition, in the formula (III), L ²⁰ represents a divalent linking group selected from the group consisting of -O-, -COO-, -OCO-, divalent aliphatic groups, and combinations thereof. In addition, -COO- represents that the carbon bonded to R ²⁰ and C=O are bonded to each other, and that R ²¹ and O are bonded, and -OCO- is the carbon bonded to R ²⁰ and O are bonded to each other, and R ²¹ and C =O indicates bonding.

Examples of the divalent aliphatic group represented by L ²⁰ include a divalent aliphatic chain group or an aliphatic cyclic group. As the divalent aliphatic chain, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. As a divalent aliphatic cyclic group, a C3-C20 cycloalkylene group is preferable, and a C3-C15 cycloalkylene group is more preferable.

Among these, as L ²⁰ , -COO- or -OCO- is preferable, and -COO- is more preferable.

In addition, in the formula (III), R ²¹ is an alkyl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (hereinafter, also referred to as "fluoroalkyl group"), or -Si ^Represents a monovalent organic group including (R ^a3 )(R ^a4 )O-, and R ^a3 and R ^a4 each independently represent an alkyl group, a haloalkyl group, or an aryl group.

In the present invention, for the reason that the adhesion of the optically anisotropic layer to be formed with the polarizer becomes better, R ²¹ in the formula (III) is preferably a fluoroalkyl group having 1 to 20 carbon atoms, and 1 to 18 carbon atoms It is more preferable that it is a fluoroalkyl group of, and it is more preferable that it is a C2-C15 fluoroalkyl group.

In addition, the number of fluorine atoms is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.

In the present invention, it is preferable that the repeating unit represented by the formula (III) is a repeating unit represented by the following formula (IV) from the viewpoint of adhesion of the formed optically anisotropic layer to a polarizer and radical polymerization.

[Formula 13]

In the formula (IV), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, similarly to R ²⁰ in the formula (III), and a suitable aspect is also the same.

In addition, in said formula (IV), ma and na each independently represent the integer of 0-19. Among them, from the viewpoint of improving adhesion and obtaining raw materials, ma is preferably an integer of 1 to 8, and more preferably an integer of 1 to 5. In addition, na is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, still more preferably an integer of 2 to 10, and most preferably an integer of 5 to 7. However, ma and na represent the integer of 0-19 in total.

In addition, in the formula (IV), X ²¹ represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

As the monomer forming the repeating unit represented by the above formula (III) or (IV), specifically, for example, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3, 3-pentafluoropropyl(meth)acrylate, 2-(perfluorobutyl)ethyl(meth)acrylate, 2-(perfluorohexyl)ethyl(meth)acrylate, 2-(perfluorooctyl) Ethyl (meth)acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5- Methylhexyl)ethyl (meth)acrylate, 2-(perfluoro-7-methyloctyl)ethyl (meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H -Octafluoropentyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, 1H,1H,9H-hexadecafluorononyl (meth)acrylate, 1H-1-( Trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth)acrylate, 3 -Perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2- Hydroxypropyl(meth)acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl(meth)acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxy And propyl (meth)acrylate.

On the other hand, as the monovalent organic group including -Si(R ^a3 )(R ^a4 )O- represented by R ²¹ in the above formula (III), it is an organic group derived from a siloxane bond, and is represented by the following formula (VII). It is more preferable that it is a structure obtained by polymerizing the compound to appear.

[Formula 14]

In the formula (VII), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^a5 represents an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In the formula (VII), R ^a3 and R ^a4 each independently represent an alkyl group, a haloalkyl group, or an aryl group.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and a hexyl group.

As the haloalkyl group, a fluorinated alkyl group having 1 to 10 carbon atoms is preferable, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.

As an aryl group, C6-C20 is preferable, and a phenyl group, a naphthyl group, etc. are mentioned, for example.

Among these, R ^a3 and R ^a4 are preferably a methyl group, a trifluoromethyl group or a phenyl group, and particularly preferably a methyl group.

In the formula (VII), m represents an integer of 10 to 1000, an integer of 20 to 500 is preferable, and an integer of 30 to 200 is more preferable.

As the compound represented by the above formula (VII), a polysiloxane macromer containing a single-terminal (meth)acryloyl group (e.g., Silaplane 0721, Copper 0725 (above, brand name, manufactured by JNC Corporation), AK-5 , AK-30, AK-32 (above, brand name, manufactured by Toa Kosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22 -164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above, brand name, manufactured by Shin-Etsu Chemical Co., Ltd.)), etc. Can be lifted.

In the present invention, the content in the case of having a repeating unit represented by the above formula (III) is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and more preferably 10 to 60% by mass with respect to all repeating units. It is more preferable that it is mass %.

In addition, in the present invention, in the case of having a repeating unit represented by the formula (III), the content of the repeating unit represented by the formula (I) because the adhesiveness of the optically anisotropic layer to be formed with the polarizer becomes better. It is 10-50 mass% with respect to this total repeating unit, The content of the repeating unit represented by the above formula (II) is 5-50 mass% with respect to all the repeating units, and the content of the repeating unit represented by the above formula (III) is all It is preferable that it is 10-60 mass% with respect to a repeating unit.

<V part>

The polymer compound of the present invention preferably has a repeating unit (V part) represented by the following formula (V) because the orientation of the liquid crystal compound described later becomes better.

[Formula 15]

In the formula (V), R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable. And a hydrogen atom or a methyl group is more preferable.

Specific examples of the monomer forming the repeating unit represented by the above formula (V) include acrylic acid and methacrylic acid.

In the present invention, the content in the case of having a repeating unit represented by the formula (V) is preferably 1 to 60% by mass, more preferably 2 to 40% by mass, and more preferably 4 to 20% by mass with respect to all repeating units. It is more preferable that it is mass %.

<Other parts>

The polymer compound of the present invention may have other repeating units other than the repeating units represented by the above-described formulas (I) (II) (III) and (V), if necessary.

As a monomer forming another repeating unit, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley Interscience (1975) Chapter 2 Page 1 to 483 can be used.

Examples include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can.

Specifically, the following monomers are mentioned.

(Acrylic acid esters)

As acrylic esters, specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl Acrylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

(Methacrylic acid esters)

As methacrylic acid esters, specifically, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane mono Methacrylate, benzyl methacrylate, methoxybenzyl methacrylate, phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol monoacetate monomethacrylate, etc. Can be lifted.

(Acrylamides)

As acrylamides, specifically, for example, acrylamide, N-alkylacrylamide (as an alkyl group, one having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group), and N,N-dialkylacrylamide ( Examples of the alkyl group include those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylacrylamide, and N-2-acetamide ethyl-N-acetylacrylamide.

(Methacrylamides)

As methacrylamides, specifically, for example, methacrylamide, N-alkyl methacrylamide (as an alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N,N-dialkyl Methacrylamide (a C1-C6 thing as an alkyl group), N-hydroxyethyl-N-methyl methacrylamide, N-2-acetamide ethyl-N-acetyl methacrylamide, etc. are mentioned.

(Allyl compound)

Specific examples of the allyl compound include allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate. , Allyl lactate, etc.), allyloxyethanol, etc. are mentioned.

(Vinyl ethers)

As vinyl ethers, specifically, for example, alkyl vinyl ether (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxy Ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, Dimethyl amino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. are mentioned.

(Vinyl esters)

Specific examples of vinyl esters include vinyl acetate, vinylbutylate, vinylisobutylate, vinyltrimethylacetate, vinyldiethylacetate, vinylvalate, vinylcaproate, vinylchloroacetate, vinyldichloroacetate. , Vinylmethoxyacetate, vinylbutoxyacetate, vinyllactate, vinyl-β-phenylbutylate, vinylcyclohexylcarboxylate, and the like.

(Dialkyl itaconic acid)

As dialkyl itaconic acid, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc. are mentioned.

(etc)

In addition, dialkyl esters or monoalkyl esters of fumaric acid; Dibutyl fumalate; Crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleonitrile, styrene, styrene macromer (AS-6S manufactured by Doa Gosei), methyl methacrylate macromer (AA- manufactured by Doa Gosei) 6) etc. are mentioned.

In the present invention, the content in the case of having other repeating units is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and more preferably 1 to 20% by mass with respect to all repeating units. Do.

1000-200000 are preferable, as for the weight average molecular weight (Mw) of the polymer compound of this invention, 1500-100000 are more preferable, and 3000-60000 are still more preferable.

The number average molecular weight (Mn) of the polymer compound of the present invention is preferably 500 to 40000, more preferably 600 to 35000, and still more preferably 600 to 30000.

The dispersion degree (Mw/Mn) of the polymer compound of the present invention is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, and still more preferably 1.00 to 10.00.

In addition, the weight average molecular weight and the number average molecular weight are values measured under the following conditions by gel permeation chromatography (GPC).

<Measurement conditions>

[Eluent] N-methyl-2-pyrrolidone (NMP)

[Device name] EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)

[Column] TSKgel SuperAWM-H (manufactured by Tosoh Corporation)

[Column temperature] 40℃

[Flow rate] 0.50ml/min

Specific examples of the polymer compound of the present invention having each of the above-described repeating units include compounds represented by the following formulas (A-1) to (A-22).

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

The content of the polymer compound of the present invention is preferably 0.0001 to 40% by mass, and 0.001 to 20% by mass, when the total solid content (total components excluding the solvent) of the liquid crystal composition of the present invention is 100% by mass. It is more preferable and it is still more preferable that it is 0.1-5 mass %.

[Liquid Crystalline Compound]

The liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type from its shape. There are also small molecule and polymer types, respectively. Polymers generally refer to those with a degree of polymerization of 100 or more (polymer physics and phase transfer dynamics, Masaozer Doi, p. 2, Shoten Iwanami, 1992).

In the present invention, any liquid crystal compound may be used, but it is preferable to use a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound (hereinafter, also referred to as "discotic liquid crystal compound") having a polymerizable group.

Here, as a polymerizable group, a (meth)acryloyl group, a styryl group, a vinyl ketone group, a butadiene group, a vinyl ether group, an oxiranyl group, an aziridinyl group, an oxetane group, etc. are mentioned, for example, Among these, a (meth)acryloyl group or a styryl group is preferable, and a (meth)acryloyl group is more preferable.

Examples of the rod-shaped liquid crystal compound include those described in [0045] to [0066] of JP 2009-217256 A, and these contents are incorporated in the present specification.

In addition, as a discotic liquid crystal compound, for example, [0025] to [0153] of JP 2006-301614 A, [0020] to [0122] of JP 2007-108732 A or JP 2010- Those described in [0012] to [0108] of 244038 are mentioned, and these contents are incorporated herein by reference.

It is preferable that the liquid crystal compound used in the present invention is fixed in a vertically aligned state in order to adjust the optical properties of the optically anisotropic layer.

For example, a layer in which a rod-like liquid crystal compound is immobilized in a vertically aligned state can function as a positive C-plate. Further, the layer in which the discotic liquid crystal compound is fixed in a vertically aligned state can function as a negative A-plate.

In addition, in the present invention, the vertical alignment means that the normal direction of the layer and the major axis direction of the liquid crystal molecules are parallel if it is a rod-shaped liquid crystal compound, and if it is a discotic liquid crystal compound, the normal direction of the layer and the disk surface of the liquid crystal molecules are parallel. It is in an orientation state.

Moreover, although it is particularly preferable that the major axis direction of the liquid crystal molecules and the disk surface of the liquid crystal molecules are parallel to the normal direction of the layer, there are cases where the alignment state of the liquid crystal molecules has more inclination. It is preferable that this inclination is within 3.5°.

[Boron compound]

The liquid crystal composition of the present invention is a compound represented by the following formula (VI) with respect to the above-described liquid crystal compound (hereinafter, " It is preferable to further contain 0.5 to 7.0 mass %) of a boron compound").

(Z)_n-L¹⁰⁰-(Q)_m (VI)

In the formula (VI), Z represents a substituent having a polymerizable group, n represents an integer of 0 to 4, and when n is 2 or more, 2 or more Z may be the same or different. Q represents a substituent containing at least one boron atom, m represents 1 or 2, and when m is 2, two Qs may be the same or different. L ¹⁰⁰ represents an n+m valent linking group. However, when n is 0 and m is 1, L ¹⁰⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyneyl group, a substituted or unsubstituted aryl A group or a substituted or unsubstituted heteroaryl group.

In the formula (VI), examples of the substituent having the polymerizable group represented by Z include (meth)acryloyl group, styryl group, vinyl ketone group, butadiene group, vinyl ether group, oxiranyl group, aziridineyl group And substituents including an oxetane group and the like.

Among these, a substituent containing a (meth)acryloyl group, a styryl group, an oxiranyl group, or an oxetane group is preferable, and a substituent containing a (meth)acrylate group or a styryl group is more preferable.

In particular, as a substituent containing a (meth)acryloyl group, a group having an ethylenically unsaturated double bond represented by the following formula (A) is preferable.

[Formula 20]

In the formula (A), R ³ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

In addition, L ¹ is a single bond, or -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an arylene group, a heterocyclic group, and these It is a divalent linking group selected from the group consisting of a combination, and among them, a single bond, -CO-NH-, or -COO- is preferable, and a single bond or -CO-NH- is particularly preferable.

In addition, in the formula (VI), L ¹⁰⁰ represents an n+m valent linking group. However, when n is 0 and m is 1, L ¹⁰⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyneyl group, a substituted or unsubstituted aryl A group or a substituted or unsubstituted heteroaryl group.

n represents the integer of 0-4, it is preferable to represent 0 or 1, and it is more preferable to represent 1. m represents 1 or 2, and it is preferable to represent 1.

In addition, as L ¹⁰⁰ , for example, a single bond or -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, alkylene group, arylene group, heteroaryl group , And a divalent linking group selected from the group consisting of combinations thereof.

Among these, as L ¹⁰⁰ , a substituted or unsubstituted arylene group is more preferable.

In addition, the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group represented by L ¹⁰⁰ have the same meaning as those represented by R ¹ and R ² in the following formula (B), and the preferred ranges are also the same. Moreover, as an example of the substituent which these groups have, at least 1 type selected from the said substituent group Y is mentioned.

In the formula (VI), Q is a substituent containing at least one boron atom, and is preferably a group capable of adsorbing and bonding to a support (eg, a polymer film).

For example, when a polymer film has a hydroxyl group or a carboxyl group on the surface by surface treatment or the like, a group capable of bonding with a hydroxyl group or a carboxyl group of the polymer film is preferable. In addition, "a group capable of adsorbing and bonding to a polymer film" means a group capable of chemical adsorption to the polymer film by interacting with a structure of a material constituting the polymer film.

Examples of the substituent containing at least one boron atom include a substituent represented by the following formula (B).

[Formula 21]

In the formula (B), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. , R ¹ and R ² may be connected to each other via an alkylene linking group, an arylene linking group, or a linking group composed of a combination thereof.

Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R ¹ and R ² include an alkyl group, an alkenyl group, or an alkynyl group which may have a substituent.

As the alkyl group, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexade Sil group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group , A linear, branched, or cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, and a 2-norbornyl group.

Specific examples of the alkenyl group include straight chains such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, and 1-cyclohexenyl group. , Branched or cyclic alkenyl groups.

Specific examples of the alkyneyl group include an ethanyl group, a 1-propyneyl group, a 1-butyneyl group, and a 1-octaynyl group.

Examples of the substituted or unsubstituted aryl group represented by R ¹ and R ² include those in which 1 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated 5-membered ring form a condensed ring, Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and a pyrenyl group are mentioned.

As the substituted or unsubstituted heteroaryl group represented by R ¹ and R ² , for example, 1 hydrogen atom on a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Excluding dogs, what made it a heteroaryl group is mentioned.

As a heteroaromatic ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxa Sol, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranyl, benzi Sooxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinazaline, naphthyridine, phenanthrol Lin, pteridine, etc. are mentioned.

Examples of the substituents R ¹ , R ² and L ¹⁰⁰ may have include monovalent non-metal groups excluding hydrogen, and are selected from, for example, substituent group Y described above.

Moreover, as R ¹ and R ² in the above formula (B), it is preferable that they are hydrogen atoms.

As the molecular weight of the compound represented by the above formula (VI), 120 to 1200 are preferable, and 180 to 800 are more preferable.

Specific examples of the compound represented by the above formula (VI) include the compounds described in paragraphs [0035] to [0040] of JP 2007-219193A, and the contents are incorporated herein by reference.

Moreover, as another specific example of the compound represented by the said formula (VI), what is represented by the following formula is mentioned.

[Formula 22]

[Formula 23]

[Formula 24]

In the present invention, the content in the case of containing the boron compound represented by the formula (VI) is preferably 0.5 to 7.0% by mass, more preferably 1 to 6% by mass, based on the above-described liquid crystal compound, It is more preferable that it is 1-5 mass %.

In addition, when multiple types of liquid crystal compounds are contained, it is a ratio with respect to the total.

[Polymerization initiator]

It is preferable that the liquid crystal composition of this invention contains a polymerization initiator.

As a polymerization initiator, a photoinitiator is preferable.

As a photoinitiator, acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Compounds, fluoroamine compounds, aromatic sulfoniums, lopine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, and the like. Specific examples of the photopolymerization initiator, preferred embodiments, and commercially available products are described in paragraphs [0133] to [0151] of JP 2009-098658 A, and can be suitably used in the same manner in the present invention.

"The latest UV curing technology" {Kyokai Joho Kijutsu Co., Ltd.} (1991), p. 159, and "ultraviolet curing system" by Kiyomi Kato (Heisei 1st year, published by Sogo Kijutsu Center), p. Various examples are also described in 65 to 148 and are useful in the present invention.

As commercially available photo-cleavable photo-radical polymerization initiators, "Irgacure 651", "Irgacure 184", "Irgacure 819", and "Irgacure 651" manufactured by BASF (manufactured by Guchiba Specialty Chemicals Co., Ltd.) Irgacure 907", "Irgacure 1870" (CGI-403/Irgacure 184=7/3 mixed initiator), "Irgacure 500", "Irgacure 369", "Irgacure 1173", "Irgacure 2959", "Irgacure 4265", "Irgacure 4263", "Irgacure 127", "OXE01", etc.; "Kayacure DETX-S", "Kayacure-BP-100", "Kayacure-BDMK", "Kayacure-CTX", "Kayacure-BMS", "Kayacure-" manufactured by Nippon Kayaku Co., Ltd. 2-EAQ", "Kayacure-ABQ", "Kayacure-CPTX", "Kayacure-EPD", "Kayacure-ITX", "Kayacure-QTX", "Kayacure-BTC", "Kayacure -MCA" and the like; Preferred examples include "Esacure (KIP100F, KB1, EB3, BP, X33, KTO46, KT37, KIP150, TZT)" manufactured by Satomer Corporation, and the like, and combinations thereof.

〔solvent〕

The liquid crystal composition of the present invention may contain a solvent from the viewpoint of workability for forming an optically anisotropic layer.

As solvents, those capable of dissolving or dispersing the above-described copolymers, liquid crystalline compounds, etc., those that tend to have a uniform surface shape in the coating process and drying process, those that can ensure liquid storage, and those that have an appropriate saturated vapor pressure It can be appropriately selected from the viewpoint of such as.

Examples of such a solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane , Tetrahydrofuran, anisole, phenitol, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclo Hexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, methyl 2-methoxyacetate, 2-ethoxyacetic acid Methyl, 2-ethoxy ethyl acetate, 2-ethoxy ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, Methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2 -Hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane , Octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, and the like, and may be used alone or in combination of two or more.

Among the above solvents, it is preferable to use at least one of methyl acetate, ethyl acetate, methyl ethyl ketone, acetone, methyl alcohol, and ethyl alcohol.

In the present invention, the content in the case of using a solvent is preferably an amount in which the concentration of the solid content of the liquid crystal composition is in a range of 5 to 80% by mass, more preferably an amount in a range of 10 to 75% by mass, 15 It is more preferable that it is an amount in the range of -70% by mass.

[Optical film]

The optical film of the present invention is an optical film having an optically anisotropic layer obtained by polymerizing the liquid crystal composition of the present invention described above.

Moreover, the optical film of this invention may have an optically anisotropic layer on a support body. Further, it is possible to adjust optical properties and mechanical properties by appropriately stretching each support in a state in which the optically anisotropic layer is laminated on the support.

In addition, the optical film of the present invention may have a single layer of the optically anisotropic layer, a laminated structure of two or more layers, and may have functional layers other than the optically anisotropic layer.

[Support]

Examples of the support include a glass substrate or a polymer film, and examples of the material of the polymer film include a cellulose polymer, a cycloolefin polymer, a polyester polymer, an olefin polymer, a (meth)acrylic polymer, and a polyamide polymer. Polymers, etc. are mentioned.

Among these, it is preferable to use a cellulose-based polymer, in particular, a polymer film (cellulose acylate-based film) using a cellulose acylate-based polymer, or a polymer film (cycloolefin-based film) using a cycloolefin-based polymer as a support.

In the present invention, the thickness of the support is not particularly limited, but in consideration of the mechanical strength and the case of storing the optical film of the present invention in a long roll form, it is preferably 5 to 100 μm, and 10 to 75 μm. It is more preferable and it is more preferable that it is 15-55 micrometers.

Moreover, in this invention, for the purpose of adjusting the surface property of a support body, it can surface-treat suitably. In order to lower the surface energy, for example, corona treatment, normal temperature plasma treatment, saponification treatment, etc. can be performed, and in order to increase the surface energy, silicone treatment, fluorine treatment, olefin treatment, and the like can be performed.

In addition, in the present invention, a release agent or the like may be previously applied to the surface of the support in order to control the adhesion to the optically anisotropic layer. For example, the optically anisotropic layer can be used after bonding with a polarizer through an adhesive or an adhesive in a post process, and then peeling off only the support.

[Optical anisotropic layer]

The optically anisotropic layer of the optical film of the present invention is an optically anisotropic layer obtained by polymerizing the liquid crystal composition of the present invention. For example, the liquid crystal composition of the present invention is coated on the support and then dried, A method of polymerization (curing) after that; It can be formed by a solution film forming method or the like.

As a coating method, specifically, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method or an extrusion coating method (die coating method ) (Refer to Japanese Unexamined Patent Application Publication No. 2003-164788), and a known method such as a microgravure coating method, and among them, a microgravure coating method and a die coating method are preferable.

About the drying and hardening method, a preferable example is demonstrated below.

In the present invention, it is effective to cure by combining irradiation with ionizing radiation and heat treatment before, simultaneously with or after irradiation.

For example, a method of performing heat treatment followed by irradiation with ionizing radiation, a heat treatment, a method of performing irradiation with ionizing radiation and heat treatment in this order, a method of performing heat treatment after irradiation with ionizing radiation, and the like.

In the present invention, as described above, it is preferable to perform heat treatment in combination with irradiation with ionizing radiation. The heat treatment is not particularly limited as long as it does not inhibit the functional film, but is preferably 40 to 150°C, more preferably 40 to 110°C.

The time required for heat treatment varies depending on the molecular weight of the components used, interactions with other components, viscosity, etc., but is preferably 15 seconds to 1 hour, more preferably 20 seconds to 30 minutes, and 30 seconds to 5 More preferably, it is minutes.

There is no restriction|limiting in particular about the kind of ionizing radiation, Although X-ray, electron beam, ultraviolet (UV), visible light, infrared light, etc. are mentioned, ultraviolet rays are widely used.

For example, if it contains an optically anisotropic layer is a UV curable component, it is preferred to cure the ultraviolet irradiation dose of ^{10mJ / cm 2 ~ 1000mJ / cm} 2 by an ultraviolet lamp. From the viewpoint of adhesion between the adhesive layer and the functional film, the total irradiation amount is more preferably 50 mJ/cm ² to 1000 mJ/cm ² .

On the other hand, in the solution film forming method, after preparing a solution obtained by dissolving the liquid crystal composition of the present invention described above in an organic solvent or water, performing a concentration step, a filtration step or the like appropriately, it is uniformly flexible on a support. Next, the less dry film is peeled off from the support, and both ends of the web are properly gripped with a clip or the like to dry the solvent in a drying zone. A curing process such as UV light irradiation can also be appropriately used. Moreover, it is also possible to separately extend the film during drying or after drying and curing are completed.

In the present invention, the polymer compound (copolymer) of the present invention contained in the liquid crystal composition of the present invention described above is, on the air interface side of the optically anisotropic layer, because the adhesiveness of the optically anisotropic layer to the polarizer becomes better, That is, it is preferable to be unevenly distributed on the opposite side of the interface with the support.

Here, the polymer compound of the present invention unevenly distributed on the air interface side is a copolymer itself having a repeating unit represented by the formula (I) (Part I) and a repeating unit represented by the formula (II) (Part II) It is not a (unreacted product), but refers to a product after the polymerizable group contained in Part I has been reacted by polymerization.

In addition, unevenness is the content of the polymer compound in a region from the surface of the optically anisotropic layer on the air interface side to 10% of the thickness of the optically anisotropic layer, rather than the total mass (average mass) of the polymer compound contained in the optically anisotropic layer. Says a lot of this.

In addition, in the present invention, when the liquid crystal composition of the present invention contains a boron compound represented by the above formula (VI), the boron compound is used as a support for the optically anisotropic layer because the adhesive property with the support for the optically anisotropic layer becomes good. It is preferable to be unevenly distributed on the side.

Here, the unevenness is the content of the boron compound in a region from the interface on the support side of the optically anisotropic layer to 10% of the thickness of the optically anisotropic layer, rather than the total mass (average mass) of the boron compound contained in the optically anisotropic layer. Says a lot of this.

In the present invention, the thickness of the optically anisotropic layer is not particularly limited, but it is preferably 0.1 to 30.0 μm, more preferably 0.2 to 5.0 μm, and still more preferably 0.4 to 2.0 μm.

When the thickness of the optically anisotropic layer is 0.1 μm or more, it is possible to ensure processing suitability and durability in the case of bonding to a polarizer, and when it is 30 μm or less, it is preferable from the viewpoint that the polarizing plate can be thinned.

[Polarizer]

The polarizing plate of the present invention has the above-described optical film of the present invention and a polarizer, and is a polarizing plate in which an optically anisotropic layer and a polarizer contained in the optical film are bonded together via an adhesive layer.

[Polarizer]

The polarizer included in the polarizing plate of the present invention is not particularly limited as long as it is a member having a function of converting light into a specific linearly polarized light, and a conventionally known absorption type polarizer and a reflection type polarizer can be used.

As the absorption type polarizer, an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer are used. The iodine polarizer and the dye polarizer include a coating type polarizer and a stretch type polarizer, and both can be applied, but a polarizer manufactured by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching is preferable.

In addition, as a method of obtaining a polarizer by stretching and dyeing in the state of a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Japanese Patent Publication No. 5048120, Japanese Patent Publication No.5143918, Japanese Patent Publication No. 4691205, and Japan Patent Publication No. 44751481 and Japanese Patent Publication No. 4771486 are mentioned, and known techniques related to these polarizers can also be preferably used.

As the reflective polarizer, a polarizer in which thin films having different birefringence are stacked, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection area and a quarter wave plate are combined, and the like are used.

Among them, a polymer containing a polyvinyl alcohol-based resin (-CH ₂ -CHOH- as a repeating unit), especially selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers, because of the better adhesiveness. It is preferable that it is a polarizer containing at least one).

In the present invention, the thickness of the polarizer is not particularly limited, but it is preferably 1 μm to 50 μm, more preferably 2 μm to 30 μm, and still more preferably 3 μm to 20 μm.

〔Adhesive layer〕

The adhesive layer of the polarizing plate of the present invention may be formed of an adhesive.

As the adhesive, an adhesive containing a resin having a hydroxyl group is preferable. In addition to a polyvinyl alcohol adhesive, an epoxy-based active energy ray-curable adhesive, for example, as shown in Japanese Laid-Open Patent Publication No. 2004-245925, In 100 parts by mass of the total amount of the (meth)acrylic compound described in Japanese Patent Laid-Open No. 2008-174667, an adhesive containing an epoxy compound that does not contain a ring and cured by heating or irradiation with active energy rays, (a) in a molecule A (meth)acrylic compound having two or more (meth)acryloyl groups, (b) a (meth)acrylic compound having a hydroxyl group in the molecule and having only one polymerizable double bond, and (c) a phenol ethylene oxide modified acrylic And active energy ray-curable adhesives containing a rate or nonylphenol ethylene oxide-modified acrylate. Among these, polyvinyl alcohol-based adhesives are most preferred.

Further, the polyvinyl alcohol-based adhesive is an adhesive containing modified or unmodified polyvinyl alcohol. The polyvinyl alcohol adhesive may contain a crosslinking agent in addition to modified or unmodified polyvinyl alcohol. As a specific example of the adhesive, an aqueous solution of polyvinyl alcohol or polyvinyl acetal (e.g., polyvinylbutyral), or a latex of a vinyl-based polymer (e.g., polyvinyl chloride, polyvinyl acetate, polybutylacrylate) may be mentioned. . A particularly preferable adhesive is an aqueous solution of polyvinyl alcohol. At this time, the polyvinyl alcohol is preferably completely saponified.

Further, the epoxy-based active energy ray-curable adhesive can be crosslinked with the copolymer according to the present invention, since the epoxy group is opened and a hydroxyl group is generated by irradiation with the active energy ray. For this reason, in the present invention, an epoxy-based active energy ray-curable adhesive can also be included as a hydroxyl group-containing adhesive, and can be appropriately used.

[Image display device]

The image display device of the present invention is an image display device having the above-described optical film or polarizing plate and an image display element.

[Image display element]

The image display device used in the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel.

Among these, it is preferable that it is a liquid crystal cell or an organic EL display panel, and it is more preferable that it is a liquid crystal cell. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as an image display element, an organic EL display device using an organic EL display panel as an image display element is preferable, and a liquid crystal display device is more preferable.

<liquid crystal cell>

The liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Alignment) mode, OCB (Optical Compensated Bend) mode, FFS or IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode, but these It is not limited to.

In the liquid crystal cell of the TN mode, when no voltage is applied, the rod-like liquid crystal molecules are substantially horizontally aligned, and further twisted to 60 to 120° and aligned. The TN mode liquid crystal cell is most often used as a color TFT (Thin Film Transistor) liquid crystal display device, and is described in a number of documents.

In the liquid crystal cell of VA mode, when no voltage is applied, the rod-like liquid crystal molecules are substantially vertically aligned. In the VA mode liquid crystal cell, (1) a liquid crystal cell in the narrow VA mode in which (1) the rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally aligned when a voltage is applied. -176625), (2) VA mode multi-domain (MVA mode) liquid crystal cell (SID97, Digest of tech.Papers (Preliminary Proceedings) 28(1997) 845) in order to enlarge the viewing angle, (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied, and multi-domain alignment is twisted when voltage is applied (preliminary proceedings of the Japan Liquid Crystal Debate 58~59 (1998) And (4) a liquid crystal cell in SURVIVAL mode (published at LCD International 98). Moreover, any of PVA (Patterned Vertical Alignment) type, optical alignment type (Optical Alignment), and PSA (Polymer-Sustained Alignment) may be used. Details of these modes are described in detail in JP 2006-215326 A and JP 2008-538819 A.

In the liquid crystal cell of the IPS mode, rod-shaped liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond planarly by applying an electric field parallel to the substrate surface. In the IPS mode, black display is displayed in the state where an electric field is not applied, and absorption axes of a pair of upper and lower polarizing plates are orthogonal. A method of improving the viewing angle by reducing the leakage light during black display in an oblique direction by using an optical compensation sheet is disclosed in Japanese Patent Application Laid-Open Nos. Hei 10-054982, Japanese Patent Laid-Open Nos. 11-202323, and Japanese Laid-Open Publications. Patent Publication No. Hei 9-292522, Japanese Unexamined Patent Publication No. 11-133408, Japanese Unexamined Patent Publication No. Hei 11-305217, Japanese Unexamined Patent Publication No. Hei 10-307291 and the like are disclosed.

<Organic EL display panel>

The organic EL display panel used as the image display element used in the present invention is a display panel constructed using an organic EL element formed by sandwiching an organic light-emitting layer (organic electroluminescence layer) between electrodes (between cathode and anode). . The configuration of the organic EL display panel is not particularly limited, and a known configuration is employed.

Example

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

[Synthesis Example 1]

<Synthesis Example of Copolymer A-5>

6.7 g of cyclohexanone and 1.7 g of isopropanol were introduced into a 300 milliliter 3-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube, and the temperature was raised to 73°C.

Then, 2-(perfluorohexyl)ethyl acrylate 12.3 g (29.3 mmol), 4-(4-acryloyloxybutoxy) benzoyloxyphenylboronic acid 5.6 g (14.7 mmol), acrylic acid 2.1 g (29.3 mmol) ), a mixed solution consisting of 26.4 g of cyclohexanone, 6.6 g of isopropanol, and 0.51 g of an azo polymerization initiator (V-601, manufactured by Wako Junyaku Co., Ltd.) was dripped at a constant speed so that the dropping was completed in 150 minutes. After completion of the dropping, the temperature was raised to 90° C., and stirring was continued for 4 hours.

Subsequently, glycidyl methacrylate 4.2 g (29.3 mmol), tetrabutylammonium bromide 1.5 g (4.7 mmol), p-methoxyphenol 0.4 g, cyclohexanone 16.2 g, and isopropanol 4.1 g were introduced at 80°C. The temperature was raised to, and stirring was continued for 8 hours to obtain 88.6 g of a cyclohexanone/isopropanol solution of a copolymer represented by the following formula (A-5) (hereinafter abbreviated as “Copolymer A-5”).

The weight average molecular weight (Mw) of this copolymer A-5 was 60,300 (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)) under the measurement conditions of eluent NMP, flow rate 0.50 ml/min, temperature 40°C. Calculated in terms of polystyrene, and the columns used were TSKgel SuperAWM-H x 3 (manufactured by Tosoh Corporation). Moreover, the acid value of the obtained copolymer A-5 was 7.3, and the residual ratio of carboxylic acid was 5 mol%.

[Formula 25]

[Synthesis Example 2]

<Synthesis Example of Copolymer A-7>

6.7 g of cyclohexanone and 1.7 g of isopropanol were introduced into a 300 milliliter 3-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction tube, and the temperature was raised to 73°C. Then, 2-(perfluorohexyl)ethyl acrylate 12.3 g (29.3 mmol), 4-(4-acryloyloxybutoxy) benzoyloxyphenylboronic acid 5.6 g (14.7 mmol), acrylic acid 2.1 g (29.3 mmol) ), a mixed solution consisting of 26.4 g of cyclohexanone, 6.6 g of isopropanol, and 0.51 g of an azo polymerization initiator (V-601, manufactured by Wako Junyaku Co., Ltd.) was dripped at a constant speed so that the dropping was completed in 150 minutes. After adding 1.3 g of 1,3-propanediol, it heated up to 90 degreeC, and continued stirring for 4 hours.

Subsequently, glycidyl methacrylate 4.2 g (29.3 mmol), tetrabutylammonium bromide 1.5 g (4.7 mmol), p-methoxyphenol 0.4 g, cyclohexanone 18.0 g, and isopropanol 4.5 g were introduced at 80°C. The temperature was raised to, and stirring was continued for 8 hours to obtain 91.9 g of a cyclohexanone/isopropanol solution of a copolymer represented by the following formula (A-7a) (hereinafter abbreviated as “copolymer A-7a”).

The weight average molecular weight (Mw) of this copolymer A-7a was 11,200 (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)) as an eluent NMP, a flow rate of 0.50 ml/min, and a polystyrene under the measurement conditions of a temperature of 40°C. Conversion calculated and used were TSKgel SuperAWM-H x 3 (manufactured by Tosoh Corporation). Moreover, the acid value of the obtained copolymer A-7a was 5.2, and the residual ratio of carboxylic acid was 3 mol%.

[Formula 26]

[Other Synthesis Examples]

Except having changed the monomer component, in the same manner as in Synthesis Example 1 or 2 described above, a copolymer represented by the following formula (A-1) (hereinafter abbreviated as "copolymer A-1"), the following formula (A Copolymer represented by -4) (hereinafter abbreviated as "copolymer A-4"), copolymer represented by the following formula (A-7b) (hereinafter abbreviated as "copolymer A-7b"), the following formula The copolymer represented by (A-7c) (hereinafter abbreviated as "Copolymer A-7c") and the copolymer represented by the following formula (A-11) (hereinafter abbreviated as "Copolymer A-11") Synthesized.

[Formula 27]

[Comparative Synthesis Example 1]

Copolymer R-1 represented by the following formula was synthesized according to the method described in paragraph [0145] of JP 2005-248116A.

[Formula 28]

[Comparative Synthesis Examples 2 to 4]

Except having changed the monomer component, in the same manner as in Synthesis Example 2 described above, a copolymer represented by the following formula (R-2) (hereinafter abbreviated as "copolymer R-2"), the following formula (R-3) The copolymer represented by) (hereinafter abbreviated as "copolymer R-3") and the copolymer represented by the following formula (R-4) (hereinafter, abbreviated as "copolymer R-4") were synthesized.

[Chemical Formula 29]

For each of the synthesized copolymers, the content (mass%) of the repeating units represented by formulas (I), (II), (III) and (V) and other repeating units is shown in Table 1 below.

[Table 1]

(Examples 1 to 9 and Comparative Examples 1 to 5)

<Production of optical film>

Each of the synthesized copolymers and the liquid crystal compounds shown in Tables 2 to 4 below were mixed in parts by mass shown in Tables 2 to 4 below to prepare a liquid crystal composition.

In addition, corona treatment was performed on one side of a cycloolefin polymer film (JSR Co., Ltd. product name: Aton film, Re = 95 nm, Rth = 100 nm, film thickness 25 μm) at a discharge amount of 125 W·min/m ² .

Then, each prepared liquid crystal composition was applied to the surface subjected to the corona treatment with a wire bar of #2.6. In order to dry the solvent of the composition and the orientation and aging of the liquid crystal compound, it was heated for 90 seconds with a warm air of 70°C.

Subsequently, ultraviolet irradiation (300 mJ/cm ² ) was performed at 40° C. at an oxygen concentration of 100 ppm under nitrogen purge, and the orientation of the liquid crystal compound was fixed to produce an optical film.

The liquid crystalline compound, alignment aid, boron compound, monomer, polymerization initiator, and leveling agent in Table 2 below each were used as shown below.

Liquid crystal compound G1

Mixture of 83:15:2 (mass ratio) of the following liquid crystalline compound (RA)(RB)(RC)

[Formula 30]

・Orientation aid H1

[Formula 31]

・Boron compound J1

[Formula 32]

Monomer K1: Biscot #360 (manufactured by Osaka Yuki Chemical High School Co., Ltd.)

Polymerization initiator L1: OXE-01 (manufactured by BASF)

·Leveling agent M1

[Formula 33]

<Production of the polarizing plate>

(Film surface treatment)

After immersing a cellulose acetate film (manufactured by Fujifilm, Fujitak TD40UC) in 1.5 mol/L aqueous sodium hydroxide solution (saponification solution) heated to 37°C for 1 minute, the film was washed with water, and then 0.05 mol/L After being immersed in an aqueous sulfuric acid solution for 30 seconds, it was further passed through a washing bath (水洗浴). Then, dehydration with an air knife was repeated three times, and after dropping water, it was kept in a drying zone at 70° C. for 15 seconds and dried to prepare a saponified cellulose acetate film.

<Production of the polarizer>

According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, a difference in circumferential speed was given between two pairs of nip rolls, and stretched in the longitudinal direction to produce a polarizer having a thickness of 12 μm.

<joining>

Using each produced optical film and the produced saponified cellulose acetate film, after placing the produced polarizer between them, using the following adhesive, roll-to-roll so that the absorption axis of the polarizer and the longitudinal direction of the film are parallel. Stacked.

Here, one surface of the polarizer was made so that the coated surface of the optical film was on the side of the polarizer, and the other surface of the polarizer was made the cellulose acetate film.

After lamination, a polarizing plate was produced by curing by drying at 70° C. for 10 minutes.

(glue)

Polyvinyl alcohol (Kurare, PVA-117H) 3% aqueous solution

[Orientation]

About the optically anisotropic layer of the produced optical film, the value of |Rth(550)| with respect to the film thickness of 1 micrometer of the optically anisotropic layer was calculated, and evaluated by the following criteria. The results are shown in Tables 2 to 4 below.

In addition, when the liquid crystal compounds are the same, the one having high alignment property increases |Rth(550)| to the film thickness of the liquid crystal layer of 1 μm.

Therefore, the orientation was evaluated by |Rth(550)| with respect to the film thickness of 1 μm of the liquid crystal layer.

A: 120nm/m or more

B: 110nm/m or more and less than 120nm/m

C: 100 nm/m or more and less than 110 nm/m

D: less than 100nm/m

Here, if the evaluation results are A, B, and C, there is no practical problem, and it is preferable that the evaluation is A.

[Face shape]

The planar shape performance of the optically anisotropic layer of the produced optical film was observed in a state in which each polarizing plate was interposed on a cross nichol.

The degree of non-uniformity was evaluated visually, and evaluated in the following four stages A to D. The results are shown in Tables 2 to 4 below.

A: No unevenness is recognized at all

B: A little unevenness is admitted, but I don't care

C: Non-uniformity is recognized, but practically no problem

D: Unevenness is strongly recognized, and I am very worried

[Adhesion]

Adhesiveness was evaluated by the crosscut method described in JIS-K-5600-5-6-1.

With respect to the produced polarizing plate, 100 crosscuts were put on the surface of the optical film at 1 mm intervals, and an adhesion test was performed with a cellophane tape (manufactured by Nichiban Corporation). It peeled after attaching a new cellophane tape, and it judged with the following criteria. The results are shown in Tables 2 to 4 below. In addition, the crosscut was produced by cutting from the cycloolefin polymer film (support) side of the optical film until it touched the surface of the polarizer.

A: No peeling of squares during crosscut

B: 50% or more and less than 100% that there is no peeling of the square during the crosscut

C: 20% or more and less than 50% of no peeling of squares during crosscutting

D: Less than 20% of no peeling of squares during crosscutting

Here, if the evaluation results are A, B, and C, there is no practical problem, and it is preferable that the evaluation is A.

[Table 2]

[Table 3]

[Table 4]

From the results shown in Tables 2 to 4, it was found that when the polymer compound of the present invention is not blended, the adhesion between the polarizer and the optically anisotropic layer may be inferior, and the orientation and planar shape may also be inferior ( Comparative Examples 1-5).

On the other hand, it was found that when the polymer compound of the present invention was blended, the orientation was excellent, the surface shape of the optically anisotropic layer to be formed was improved, and the adhesion to the polarizer was also improved (Examples 1 to 9). .

Particularly, from the contrast between Example 3 and Example 4, it was found that the alignment of the liquid crystal compound becomes more favorable if it has a repeating unit (V part) represented by the above formula (V).

Further, from the contrast between Example 5 and Example 6, it was found that when the boron compound represented by the above formula (VI) is blended, the adhesiveness to the polarizer becomes better.

In addition, from the comparison of Examples 7 to 9, the content of the repeating unit represented by the formula (I) is 10 to 50 mass% with respect to the total repeating units, and the content of the repeating unit represented by the formula (II) is all repeating units. It was found that the adhesiveness to the polarizer was better when the content of the repeating unit represented by the formula (III) was 10 to 60% by mass relative to the total repeating unit.

Claims (19)

A copolymer having a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II), and a liquid crystal compound,
The weight average molecular weight of the copolymer is 1000 to 200000,
The content of the repeating unit represented by the following formula (I) in the copolymer is 5 to 80 mass% with respect to all repeating units,
The liquid crystal composition, wherein the content of the repeating unit represented by the following formula (II) in the copolymer is 3 to 80% by mass based on all repeating units.

Here, in the formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ² -, -NR ² COO-, -CR ² N-, a substituted or unsubstituted divalent aliphatic group , A substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of combinations thereof, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or -X ¹ -P ¹ . P ¹ represents a polymerizable group.
In addition, in the formula (II), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R ¹¹ and R ¹² may be connected to each other through a linking group consisting of an alkylene linking group, an arylene linking group, or a combination thereof. X ¹⁰ is a single bond, or -O-, -S-, -COO-, -OCO-, -CONR ¹³ -, -NR ¹³ COO-, -CR ¹³ N-, a substituted or unsubstituted divalent aliphatic group , A substituted or unsubstituted divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof, and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The method according to claim 1,
The liquid crystal composition, wherein the copolymer further has a repeating unit represented by the following formula (III).

Here, in the formula (III), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ²¹ represents an alkyl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a monovalent organic group including -Si(R ^a3 )(R ^a4 )O-, and R ^a3 and R ^a4 each independently represent an alkyl group, a haloalkyl group, or an aryl group. L ²⁰ represents a divalent linking group selected from the group consisting of -O-, -COO-, -OCO-, divalent aliphatic groups, and combinations thereof. The method according to claim 2,
The liquid crystal composition in which R ²¹ in the formula (III) is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. The method of claim 3,
The liquid crystal composition in which the repeating unit represented by the formula (III) is a repeating unit represented by the following formula (IV).

Here, in the above formula (IV), R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ma and na each independently represent the integer of 0-19. However, ma and na represent the integer of 0-19 in total. X ²¹ represents a hydrogen atom or a fluorine atom. The method according to any one of claims 2 to 4,
In the copolymer, the content of the repeating unit represented by the formula (I) is 10 to 50 mass% with respect to all repeating units, and the content of the repeating unit represented by the formula (II) is 5 to 50 mass with respect to all repeating units. %, and the content of the repeating unit represented by the formula (III) is 10 to 60 mass% with respect to all repeating units. The method according to any one of claims 1 to 4,
The liquid crystal composition, wherein the polymerizable group represented by P ¹ in the formula (I) is any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-7).

Here, in the formulas (P-1) to (P-7), * represents a bonding position with X ¹ . R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and two R ³ may be the same or different, and may be connected to each other to form a ring structure. The method according to any one of claims 1 to 4,
The liquid crystal composition, wherein the copolymer further has a repeating unit represented by the following formula (V).

Here, in the formula (V), R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The method according to any one of claims 1 to 4,
The liquid crystal composition, wherein the liquid crystal compound is a rod-shaped liquid crystal compound having a polymerizable group or a disk-shaped liquid crystal compound having a polymerizable group. The method according to claim 1,
A liquid crystal composition containing 0.5 to 7.0 mass% of a compound represented by the following formula (VI) with respect to the liquid crystal compound.
(Z) _n -L ¹⁰⁰ -(Q) _m (VI)
Here, in the formula (VI), Z represents a substituent having a polymerizable group, n represents an integer of 0 to 4, and when n is 2 or more, 2 or more Z may be the same or different. Q represents a substituent containing at least one boron atom, m represents 1 or 2, and when m is 2, two Qs may be the same or different. L ¹⁰⁰ represents an n+m valent linking group. However, when n is 0 and m is 1, L ¹⁰⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyneyl group, a substituted or unsubstituted aryl A group or a substituted or unsubstituted heteroaryl group. The method according to any one of claims 1 to 4,
X ¹ in Formula (I) is -O-, -S-, -COO-, -OCO-, -CONR ² -, -NR ² COO-, -CR ² N-, substituted or unsubstituted divalent A liquid crystal composition which shows a divalent linking group selected from the group consisting of an aliphatic group, a substituted or unsubstituted divalent aromatic group, and a combination thereof.
However, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or -X ¹ -P ¹ , and P ¹ represents a polymerizable group. The method according to any one of claims 1 to 4,
The liquid crystal composition in which the polymerizable group represented by P ¹ in the formula (I) is any one polymerizable group selected from the group consisting of groups represented by the following formulas (P-1) to (P-3).

Here, in the formulas (P-1) to (P-3), * represents a bonding position with X ¹ . An optical film having an optically anisotropic layer obtained by polymerizing the liquid crystal composition according to claim 1. The method of claim 12,
An optical film having a support and the optically anisotropic layer provided on the support. The method of claim 13,
The optical film in which the copolymer contained in the liquid crystal composition according to any one of claims 1 to 4 is unevenly distributed on the air interface side of the optically anisotropic layer. The method of claim 13,
The optically anisotropic layer is an optically anisotropic layer obtained by polymerizing the liquid crystal composition according to claim 9,
An optical film in which the compound represented by formula (VI) contained in the liquid crystal composition according to claim 9 is unevenly distributed on the support side of the optically anisotropic layer. The method of claim 13,
The optical film, wherein the support is a cellulose acylate-based film or a cycloolefin-based film. Having the optical film according to claim 12 and a polarizer,
A polarizing plate in which an optically anisotropic layer included in the optical film and the polarizer are bonded together through an adhesive layer. An image display device comprising the optical film according to claim 12 and an image display element. An image display device comprising the polarizing plate according to claim 17 and an image display element.